Low-boiling hydrocarbons, such as methane, ethane, propane, butane and iso-butane, are present in natural gas and also in crude oil. Because water may also be present in varying amounts in natural gas and crude oil, the mixture, under conditions of elevated pressure and reduced temperature, tends to form gas hydrate crystals. Gas hydrates are clathrates (inclusion compounds) of gases in a lattice consisting of water molecules. The maximum temperature at which gas hydrates can be formed strongly depends on the pressure of the system. For example, ethane at a pressure of approximately 1 MPa can form hydrates only at temperatures below 4.degree. C. whereas at a pressure of 3 MPa stable hydrates can be present at temperatures as high as 14.degree. C. With respect to this strong dependence of the hydrate melting point on pressure, hydrates markedly differ from ice.
As described by M. von Stackelberg and H. R. Muller (Z. Electrochem., 58, 25 (1954)), methane and ethane hydrates form cubic lattices having a lattice constant of 1.2 nm (hydrate structure I). The lattice constant of the cubic propane and butane gas hydrates is 1.73 nm (hydrate structure II). However, the presence of even small amounts of propane in a mixture of low-boiling hydrocarbons will result in the formation of gas hydrates having structure II (J. H. van der Waals and J. C. Platteeuw, Adv. Chem. Phys. 2, 1 (1959)).
It has been known for a long time, that gas hydrate crystals, when allowed to form and grow inside a conduit such as a pipeline, tend to block or even damage the conduit. To prevent such blocking, the following measures are possible in principle: removal of free water; maintaining elevated temperatures and/or reduced pressures or the addition of melting point depressants (antifreezes). In practice, antifreezes are most frequently used. However, antifreezes, such as the lower alcohols and glycols, have to be added in substantial amounts to be effective, typically several tens of percent by weight of the water present. A disadvantage of such amounts is the cost of the antifreeze. A further disadvantage is that recovery is relatively expensive.
An attractive alternative to the anti-hydrate measures described above, particularly the antifreezes, is to use a crystal growth inhibitor.
Plants and poikilothermic animals such as insects and cold-water fish are known to protect themselves from freezing; both by antifreezes such as glycols and by special peptides and glycopeptides (termed antifreeze proteins and antifreeze glycoproteins) that interfere with ice crystal growth (A.L. de Vries, Comp. Biochem. Physiol, 73, 627 (1982)). Although we found such cold-water fish peptides and glycopeptides to be effective in interfering with the growth of gas-hydrate crystals, their production and use for this purpose are currently considered to be uneconomical.
In International Patent Application Publication WO 93/25798 the use of polymers and copolymers of N-vinyl-2-pyrrolidone for inhibiting the formation, growth and/or agglomeration of gas hydrate crystals is disclosed.
U.S. Pat. No. 5,460,728 discloses hydrate inhibition compounds that include ammonium alkyls having at least three alkyl groups of four or more carbon molecules. This patent includes examples of ammoniumalkyls, but does not include any examples of ammonium alkyls having two alkyl groups that have greater than ten carbon atoms. The ammonium alkyls disclosed in this patent are effective compared to the prior art hydrate inhibitors know at that time, but there remains a need for even more effective hydrate inhibitors. For example either greater depression of temperatures at which hydrates plug flowlines and/or effectiveness at lower concentrations would be desirable.
It is therefore an object of the present invention to provide a method to inhibit formation of hydrates in streams containing at least some light hydrocarbons and water. It is a further object to provide such a method wherein a high concentration of additive is not required.